US3404105A - Foaming process for polyurethane in the presence of pore regulators - Google Patents

Foaming process for polyurethane in the presence of pore regulators Download PDF

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Publication number
US3404105A
US3404105A US431435A US43143565A US3404105A US 3404105 A US3404105 A US 3404105A US 431435 A US431435 A US 431435A US 43143565 A US43143565 A US 43143565A US 3404105 A US3404105 A US 3404105A
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United States
Prior art keywords
foam
pore
foaming
groups
weight
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Expired - Lifetime
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US431435A
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English (en)
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Rossmy Gerd
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Evonik Operations GmbH
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TH Goldschmidt AG
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers

Definitions

  • R is hydrogen or hydrocarbon, OR wherein R is hydrocarbon,
  • This invention generally relates to polyurethane foams and is particularly directed to an improvement in manufacturing processes for flexible or elastomeric polyurethane foams produced by the reaction of polyols, polyiso 'cyanates and water in the presence of catalysts and surface active agents acting as foam stabilizers.
  • the improvement of this invention is generally applicable to prior art manufacturing processes for such foams, including those wherein the foaming is effected in the presence of additional agents or additives such as expanding or blowing agents, pigments, softeners and the like.
  • Another object of this invention is to provide a process of the indicated kind which enables the formation of larger or smaller pores in a controlled manner throughout the foam structure or within restricted zones thereof and which also renders possible the formation of zones wherein the foam is collapsed.
  • Another object of this invention is to provide for a foaming process which is carried out in the presence of both a foam stabilizer and a pore regulating agent of a novel kind to obtain a foam which has a controlled cellular pattern and resembles the cell structure of natural sponge.
  • Another object of this invention is to provide a process of the indicated kind which is simple to carry out without elaborate equipment and which can be performed at the customary concentrations of foam stabilizers.
  • the foaming with polyols, polyisocyanates and water in the presence of catalysts and surface active foam stabilizers is carried out, in accordance with this invention, in the presence of pore regulators in the form of liquid organopolysiloxanes having terminal OH groups or groups which readily hydrolize under the conditions which prevail in the foaming system.
  • organopolysiloxanes are eminently suitable for effectively controlling and adjusting the pore or cellular structure of the foam.
  • the organopolysiloxanes of the indicated kind are added to the foaming system in liquid or moderately viscous form. It should be emphasized at this point that the organopolysiloxanes which are admixed with the foaming system in accordance with this invention do not exert any foam stabilizing activity but their effect is in fact to the contrary since they have a pronounced foam destroying activity causing the foam to collapse in those regions or zones where the organopolysiloxanes are effectively incorporated into the system.
  • the inventive pore regulating effect of the organopolysiloxanes is rather contingent on the presence of surface active foam stabilizers such as the prior. art. water-soluble. polyether-modified silicone-oils.
  • organopolysiloxanes which are employed in accordance with this invention as poreregulators may be generically represented by the average Formula A wherein R stands for hydrogen or hydrocarbon, preferably methyl or another lower alkyl; x has a value of from 1.0 to 2.1, preferably 1.85 to 2.0; y has a value of from 0.01 to 1.0, preferably 0.05 to 0.3; and x-l-y is equal to 1.55 to 3, preferably 1.9 to 2.1.
  • Z may be OH, in which event the polysiloxanes could generically be represented by the Formula I wherein R, y and x have the above-indicated meaning.
  • the organopolysiloxanes may instead have terminal groups which are readily hydrolizable under the conditions of the foaming process, to wit, the terminal groups may consist of acyloxy of the formula Rfi-O- o the alkoxy group OR or the amino groups R! A I wherein R has the above meaning.
  • organopolysiloxanes may contain, for example, terminal OH groups which are partially replaced by one or several of the other indicated terminal groups.
  • the pore regulating compounds are preferably employed in the form of aqueous solutions or dispersions if the amount of such hydrolizable groups, to wit, the acyloxy, alkoxy or amino groups, is greater than the portion of SiOH groups in the polysiloxane.
  • the pore regulating polysiloxanes of this invention are liquid, oil-like substances of moderate viscosity.
  • those polysiloxanes are preferred which at normal or room temperature exhibit a viscosity of less than 1,000 cp.
  • the polysiloxanes to be used in accordance with this invention are readily incorporated into the foaming system and the results are reproducible in a reliable manner.
  • the concentration of foam stabilizers in the system need not be increased in spite of the presence of the inventive polysiloxanes.
  • the field of applicability is also much broader than that for the prior art compounds.
  • spongeli'ke pore structures can thus be easily obtained by the admixture of the inventive polysiloxanes, but uniform pore enlargement can also readily be achieved.
  • the nature and magnitude of the pore changing efiect are, of course, largely dependent on the specific foam formulation.
  • the manner of incorporating the polysiloxanes into the reaction mixture and the concentration of the polysiloxanes in the mixture are factors to be considered. These factors have to be determined for the individual systems. Generally speaking, it may be stated that the effect is the stronger and also the more restricted to a particular zone within the foam mixture, the less intense the mixing of the polysiloxane with the remaining reaction components. Thus, if the liquid organopolysiloxane is added to a particular zone of the reaction mixture and is not thorough ly and homogeneously distributed throughout the system, local enrichment of the polysiloxane within said zone will take place which causes a greater foam regulating effect than in those regions of the system which are reached by lesser amounts of polysiloxane.
  • a more uniform pore structure is desired in which the pores are slightly enlarged, i.e. the pore structure is coarser.
  • This can also be obtained by the inventive pore regulators.
  • the use of the foam stabilizers which are presently available on the market generally results in the formation of a very fine pore structure. While this is desirable for many purposes, there are situations in which such fine pore structure is disadvantageous. This applies, for example, to foaming in molds, wherein a very fine pore structure results in insufficient stability of the final foam. Thus, extended fissures, cracks and crazes may formed in the foam structure. This phenomenon is also well known from block foaming.
  • the polysiloxanes which are lowmolecular compounds, displace the foam stabilizer at and from the boundary surface and that they react, during the foaming procedure, with isocyanates under formation of higher molecular and, in some instances, resin-like solid and incompatible organopolysiloxanes. These reaction products cause then a local collapse of the foam.
  • the collapsing effect is the stronger the higher the concentration of the inventive polysiloxanes and the more irregular, that is, the more sponge-like, the more non-uniform the siloxane distribution throughout the system.
  • inventive pore regulators for the purpose of obtaining a uniform and relatively insignificant enlargement of the pore structure, generally 0.001 to 0.01 part by weight of inventive polysiloxane per 100 parts by weight of polyol are sufficient.
  • larger amounts of the organopolysiloxanes should be used which generally should be in the range of 0.01 to 0.15 part by weight of organopolysiloxane per 100 parts by weight of polyol.
  • the pore regulating effect of the inventive organopolysiloxanes is particularly pronounced in one-step foaming processes.
  • polyethers and polyesters may be used as polyols, but polyethers are preferred.
  • polyethers are preferred.
  • the addition products of the above oxides with dior multivalent alcohols and phenols, formed in alkaline or acidic media, are also suitable reactants.
  • Such alcohols and phenols may be exemplified by ethylene glycol, diethylene glycol, polyethylene glycols, propanediol-(1,2), propanediol-( 1,3), butanediols, alkanediols, butene-2-diol-(l,4), butane-2-diol-(l,4), glycerin, butanetriols, hexanetriols, pentaerythrite, trimethylol propane, hydroquinone, 4,4'-dioxydiphenylmethane, 4,4'-dioxydiphenyldimethylmethane, 4,4 dioxydicyclohexylmethane, 4,4-dioxydicyclohexylmethane, 4,4'-dioxydicyclohexyldimethylmethane and dioxynaphthaline.
  • ethylene oxide may also be used as mixing component in the polymerization or addition up to about 30%. In doing so, the incorporation of the ethylene oxide may be'elfected both by mixed polymerization and also by subsequent addition polymerization.
  • polyalkyleneglycolethers may also be employed in mixture with other multivalent hydroxyl compounds as, for example, in mixture with ethylene glycol, 1,4-butylene glycol, glycerin, trimethylolpropane, pentaerythrite, tartaric acid esters, castor oil and the like.
  • the foaming may also be performed with mixtures of such compounds or with such mixtures which additionally contain polyesters.
  • isocyanate groups aliphatic, araliphatic or aro- 'matic polyisocyanates, as, for example phenylene diisocyanates, 2,4- or 2,6-toluylene diisocyanate, diphenylmethane, 4,4-diisocyanate, diphenyl-4,4'-diisocyanate, 1,5- naphthylene diisocyanate, hexamethylene diisocyanate or decamethylene diisocyanate.
  • aliphatic, araliphatic or aro- 'matic polyisocyanates as, for example phenylene diisocyanates, 2,4- or 2,6-toluylene diisocyanate, diphenylmethane, 4,4-diisocyanate, diphenyl-4,4'-diisocyanate, 1,5- naphthylene diisocyanate, hexamethylene diisocyanate or decamethylene diisocyanate.
  • polyisocyanates and alcohols which contain free NCO groups are suitable, The following compounds may be mentioned as examples for such alcohols: trimethylolpropane, glycerin, hexanetriols, glycols.
  • addition products of polyisocyanates and lower polyesters or castor oil come into consideration.
  • reaction products of the above isocyanates with acetals according to German Patent 1,072,385 as well as the isocyanates mentioned in German Patents 1,022,789 and 1,027,394 may be used. Of course, mixtures thereof may also be employed.
  • the polyurethane foams were produced as follows: 99.9 parts by weight of a polyether, obtained by the addition of propylene oxide to glycerin, and having a hydroxyl number of 54.5 were well mixed with 0.1 part by weight of dibutyltindilaurate as catalyst.
  • the polyether-dibutyltindilaurate mixture was thereafter stirred with a solution of 0.2 part by weight of triethylenediamine and 1 part by weight of a water soluble silicone oil in 3.6 parts by weight of water.
  • the silicone oil was the foam stabilizer. This foam stabilizer corresponded to the following formula:
  • ZOH is an addition product of a mixture of 60% by weight of propylene oxide and 40% by weight of ethylene oxide with n-butanol. The average molecular weight of the compound was 1,720.
  • 47.2 parts by weight of toluylene diisocyanate (2,4 and 2,6 isomers in the ratio 80:20) were added to the system.
  • the agitator operated at ,a speed of about 3,500 r.p.rn.
  • the foaming mixture was poured into a carton or box and after completion of the reaction was hardened in a drying ovenat about 120?
  • C. 400 g. polyether were used for eachof the foaming tests.
  • the foam body or block thus obtained had a base surface of 28-28 cm.
  • Example I In this test series, a pore regulator in the form of a polysiloxane of the general Formula V was used:
  • Example II The polysiloxane of Example I with terminal hydroxyl groups was replaced bythe analogous substance, wherein the hydroxyl groups were replaced by terminal acetoxy groups. 0.02 part by weight of this polysiloxane per 100 .8 parts byweight of polyether were added to the system without any mechanical mixing. In this manner, a uniform foam of a relatively coarser, pore structurewas obtained. The height of the foam was 22.5 cm.
  • Example III- The 'procedure'of Example II was repeated, but the same amount of the polysiloxane with terminal acetoxy groups was first dissolved in'the aqueous'foam stabilizer solution and the thus enriched foam stabilizer solution was then added to the system. In this manner, a sponge-like foam of about 22 cm. height was obtained The amount of triethylenediamine was increased to 0.22 part by weight. While specific embodiments of the invention have been shown and described in detail to illustrate the application of the inventive principles, it'will be understood that the invention may be embodied otherwise without departing from' such principles.
  • a foaming process for preparing elastomeric polyurethane foam from a reaction mixture of polyols, organic polyisocyanates and water, said polyols being selected from the group consisting of polyether polyols and polyester polyols wherein the foam is stabilized by a surface active agent admixed with said reaction mixture, the improvement which comprises that said reaction mixture, in addition to said foam stabilizing surface active agent, is admixed with a minor amount of a pore regulator for the foam, said pore regulator being liquid organopolysiloxane having a viscosity at room temperature of less than 1,000 cp. and being of the average formula wherein R is hydrocarbon; Z is selected from the group consisting of wherein R' is selected from the group consisting of hydrogen and hydrocarbon,
  • R has the above meaning, and (e) mixtures of (a) (b) (c) and (d);
  • organopolysiloxane has the formula HO[SIiO:IH R n wherein R has the above meaning and n has a value of between 2 and 300.
  • organopolysiloxane has the formula:
  • R is hydrocarbon; Z is selected from the group consisting of wherein R is selected from the group consisting of hydrogen and hydrocarbon,
  • R-residues essentially consist of CH 12.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
US431435A 1964-02-24 1965-02-09 Foaming process for polyurethane in the presence of pore regulators Expired - Lifetime US3404105A (en)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
DEG39929A DE1215921B (de) 1964-02-24 1964-02-24 Verfahren zur einstufigen Herstellung von flexiblen Polyurethanschaumstoffen

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US3404105A true US3404105A (en) 1968-10-01

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BE (1) BE660101A (en))
DE (1) DE1215921B (en))
FR (1) FR1468679A (en))
GB (1) GB1028810A (en))

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472341A (en) * 1983-07-05 1984-09-18 The Upjohn Company Polyurethane process using polysiloxane mold release agents
JPS63273663A (ja) * 1987-05-02 1988-11-10 Nhk Spring Co Ltd アスファルトを含有したポリウレタン発泡体の製造方法
US4957944A (en) * 1989-06-16 1990-09-18 Union Carbide Chemicals And Plastics Company Inc. Urethane catalysts
US5162384A (en) * 1991-09-13 1992-11-10 Minnesota Mining And Manufacturing Company Making foamed plastic containing perfluorinated heterocyclic blowing agent
US5210106A (en) * 1991-10-04 1993-05-11 Minnesota Mining And Manufacturing Company Fine-celled plastic foam containing fluorochemical blowing agent
US5211873A (en) * 1991-10-04 1993-05-18 Minnesota Mining And Manufacturing Company Fine-celled plastic foam containing fluorochemical blowing agent
US5650449A (en) * 1995-04-26 1997-07-22 Mukuno; Torahiko Defoaming agent for polyurethane foam

Families Citing this family (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2221811A1 (de) * 1972-05-04 1973-11-22 Bayer Ag Verfahren zur herstellung von flammfesten urethangruppen aufweisenden schaumstoffen
FR2193049B1 (en)) * 1972-07-20 1974-12-27 Rhone Poulenc Sa
US4554295A (en) * 1983-07-13 1985-11-19 Eastern Foam Products, Inc. Method for preparing flexible polyurethane foams from polymer/polyols and improved polyurethane foam product
US5192812A (en) * 1991-02-12 1993-03-09 Union Carbide Chemicals & Plastics Technology Corporation Cell openers for urethane foam surfactants

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1122698B (de) * 1960-06-10 1962-01-25 Bayer Ag Verfahren zur Herstellung von Urethangruppen enthaltenden Schaumstoffen
US3243475A (en) * 1960-05-27 1966-03-29 Bayer Ag Polyurethanes
US3272762A (en) * 1960-10-19 1966-09-13 Ici Ltd Preparation of cellular polyurethanes in the presence of a siloxane-oxyalkylene copolymer
US3278465A (en) * 1962-06-28 1966-10-11 Ici Ltd Manufacture of cellular polyurethane materials in the presence of a polysiloxane stabilizer

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1110857B (de) * 1958-11-12 1961-07-13 Bayer Ag Verfahren zur Herstellung von Urethangruppen enthaltenden Schaumstoffen
GB907971A (en) * 1960-05-20 1962-10-10 Ici Ltd Improvements in or relating to the manufacture of foamed polyurethane materials

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3243475A (en) * 1960-05-27 1966-03-29 Bayer Ag Polyurethanes
DE1122698B (de) * 1960-06-10 1962-01-25 Bayer Ag Verfahren zur Herstellung von Urethangruppen enthaltenden Schaumstoffen
GB973234A (en) * 1960-06-10 1964-10-21 Bayer Ag Cellular polyurethanes
US3272762A (en) * 1960-10-19 1966-09-13 Ici Ltd Preparation of cellular polyurethanes in the presence of a siloxane-oxyalkylene copolymer
US3278465A (en) * 1962-06-28 1966-10-11 Ici Ltd Manufacture of cellular polyurethane materials in the presence of a polysiloxane stabilizer

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4472341A (en) * 1983-07-05 1984-09-18 The Upjohn Company Polyurethane process using polysiloxane mold release agents
JPS63273663A (ja) * 1987-05-02 1988-11-10 Nhk Spring Co Ltd アスファルトを含有したポリウレタン発泡体の製造方法
US4957944A (en) * 1989-06-16 1990-09-18 Union Carbide Chemicals And Plastics Company Inc. Urethane catalysts
US5162384A (en) * 1991-09-13 1992-11-10 Minnesota Mining And Manufacturing Company Making foamed plastic containing perfluorinated heterocyclic blowing agent
US5210106A (en) * 1991-10-04 1993-05-11 Minnesota Mining And Manufacturing Company Fine-celled plastic foam containing fluorochemical blowing agent
US5211873A (en) * 1991-10-04 1993-05-18 Minnesota Mining And Manufacturing Company Fine-celled plastic foam containing fluorochemical blowing agent
US5650449A (en) * 1995-04-26 1997-07-22 Mukuno; Torahiko Defoaming agent for polyurethane foam

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FR1468679A (fr) 1967-02-10
GB1028810A (en) 1966-05-11
BE660101A (en))
DE1215921B (de) 1966-05-05

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